JP3894968B2 - Composition for reinforcing thermoplastic polymers exhibiting improved anti-caking properties and fluidity comprising precipitated silica - Google Patents
Composition for reinforcing thermoplastic polymers exhibiting improved anti-caking properties and fluidity comprising precipitated silica Download PDFInfo
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Abstract
Description
【０００１】
【発明の属する技術分野】
本発明は、改善された凝結防止特性及び流動性を示し、少なくとも１種の沈降シリカを含んでいる熱可塑性ポリマー強化用組成物に関する。
【０００２】
本発明は特に、ブタジエン及び／又はアクリル酸エステルから誘導されるコポリマー、及び沈降シリカを含み得る塩化ビニルポリマー強化用組成物に関する。
【０００３】
【従来の技術及び発明が解決しようとする課題】
ある種の合成樹脂、特にポリ塩化ビニル又は塩化ビニル含量の多いコポリマーを主成分とする樹脂は、特に低コストでありまた良好な物理的及び／又は化学的性質を示すために建築産業で広く使用されている。
【０００４】
にもかかわらず、前記樹脂は、室温もしくは低温での衝撃強さが低く、エージング後でもその衝撃強さは低い。
【０００５】
一般に多少のエラストマー特性を示すポリマーである衝撃添加剤と称する物質を前記熱可塑性樹脂に配合することによりこれらの欠点を克服することが提案されている。
【０００６】
これらの衝撃添加剤中のエラストマーの重量は広範囲で変動し得、一般に４０％〜７０％である。しかしながら、効果を高めるために衝撃添加剤中のこのエラストマー重量を増したいとしても、添加剤を粉末形態で単離したとき、更には貯蔵中に、かなりの凝結が確認される。
【０００７】
このため、取り扱いが困難となり、空気コンベヤによる添加剤の輸送が不可能となる。
【０００８】
米国特許第３ ９８５ ７０３号は、エラストマー部分の含量が５５〜８５％であり、改善された凝結防止特性及び流動性を示すコア／シェルアクリルポリマー粉末の製造を可能とする方法を記載している。
【０００９】
前記方法は、特に前記粉末の噴霧乾燥時に、粒子直径が０．０１２ミクロンの超微粉シリカの不活性粒子０．０１〜１．５％を添加することからなる。
【００１０】
【課題を解決するための手段】
現在では、少なくとも１種の衝撃添加剤を含み、改善された凝結防止特性及び流動性を示し、更に沈降シリカを含んでいることを特徴とする熱可塑性ポリマー強化用組成物が知見されている。
【００１１】
【発明の実施の形態】
本発明では、沈降シリカとは、約１０〜６０ｎｍの一次粒子が会合して、平均寸法が３〜１００ミクロンの凝集物を形成するシリカを意味する。
【００１２】
平均寸法が３〜８０ミクロンの、好ましくは５〜６０ミクロンの凝集物を含む沈降シリカを使用することが好ましい。
【００１３】
１０００℃で２時間焼成した物質に対して測定したＳｉＯ2含量は９８％以上である。
【００１４】
本発明によれば、比表面積（ＢＥＴ）が２５〜７００ｍ2／ｇ、好ましくは５０〜５００ｍ2／ｇの沈降シリカを使用する。
【００１５】
本発明によれば、更に疎水性及び親水性両方の沈降シリカを使用する。
【００１６】
このような沈降シリカの沈殿は文献に記載されており、本発明の主題ではない。
【００１７】
本発明で使用できる衝撃添加剤の例としては特に、ブタジエン−スチレン熱可塑性樹脂（例えばアクリロニトリル−ブタジエン−スチレン樹脂（ＡＢＳ樹脂）、メタクリル酸アルキルエステル−ブタジエン−スチレン樹脂（ＭＢＳ樹脂）、及びアクリル酸及び／又はメタクリル酸アルキルエステルーブタジエン−スチレン樹脂）の中から選択されるブタジエン又はイソプレンのような共役ジエンから誘導されるグラフトコポリマーを挙げることができる。メタクリル酸アルキルエステル樹脂の中では特に、メチルメタクリレート−ブタジエン−スチレン樹脂、エチルメタクリレート−ブタジエン−スチレン樹脂、ブチルメタクリレート−ブタジエン−スチレン樹脂及びラウリルメタクリレート−ブタジエン−スチレン樹脂を挙げることができる。アクリル酸アルキルエステル−ブタジエン−スチレン樹脂に関しては、メチル、エチル、ブチル又は２−エチルヘキシルアクリレートから誘導される樹脂を挙げることができる。更には、共役ジエンとＣ2−Ｃ12アルキルアクリレートとのランダムコポリマーからなる主鎖に、Ｃ1−Ｃ4アルキルメタクリレートとＣ1−Ｃ8アルキルアクリレートとのコポリマーの鎖がグラフトしているグラフトコポリマーを挙げることができる。この主鎖コポリマーは更に、少なくとも２個のＣＨ2＝Ｃ＜基を含む架橋剤から誘導される単位を含み得る。このコポリマーは例えばフランス特許第２ ５５１ ４４６号及び第２ ５５１ ４４７号に記載されており、同特許の内容は参考として本明細書に組み入れる。
【００１８】
ブタジエンから誘導され、処理中及び加硫前には熱可塑性の樹脂（例えばスチレン−ブタジエンゴム（ＳＢＲ）、ニトリル−ブタジエンゴム（ＮＢＲ）及びアクリレート−ブタジエンゴム（ＡＢＲ））を使用することもできる。
【００１９】
ブタジエンから誘導されるこれらのポリマーの中では、ＭＢＳ及びＡＢＳ樹脂が好ましい。
【００２０】
本質的にアクリル樹脂、即ち９０重量％以上の重合アクリル酸エステルを含む樹脂を使用することもできる。
【００２１】
本発明によれば、ポリマー衝撃添加剤中のエラストマー含量は少なくとも６０重量％、好ましくは７０〜９０重量％である。
【００２２】
本発明の強化用組成物は、少なくとも８０重量％、好ましくは９５〜９９重量％の衝撃添加剤と、２０重量％以下、好ましくは１〜５重量％の沈降シリカとを含んでなる。
【００２３】
衝撃強さ改善のために本発明の沈降シリカを配合できる熱可塑性ポリマーは特に、多縮合物タイプのポリマー（とりわけポリブチレンテレフタレートのようなポリエステル、ポリカーボネート、ポリアミド）又は例えばポリメタクリレート、特にポリメチルメタクリレートのようなポリマータイプのポリマーからなり得る。熱可塑性ポリマーは、任意に過塩素化されてもよい塩化ビニルホモポリマー、及び塩化ビニルと１種以上のエチレン不飽和コモノマーとの共重合により得られ、少なくとも８０重量％の重合塩化ビニルを含んでいるコポリマーからなる群の中から選択される１種以上の付加ポリマーからなってもよい。このようなコポリマーの製造に特に適したコモノマーは、ビニリデンハライド（例えば塩化ビニリデン又はフッ化ビニリデン）、ビニルカルボキシレート（例えば酢酸ビニル、プロピオン酸ビニル及び酪酸ビニル）、アクリル酸及びメタクリル酸、これらから誘導されるニトリル、アミド及びアルキルエステル（特にアクリロニトリル、アクリルアミド、メタクリルアミド、メチルメタクリレート、メチルアクリレート、ブチルアクリレート、エチルアクリレート、２−エチルヘキシルアクリレート）、ビニル芳香族誘導体（例えばスチレン及びビニルナルタレン）、並びにオレフィン（例えばビシクロ（２．２．１）−２−ヘプテン、ビシクロ（２．２．１）ヘプタ−２，５−ジエン、エチレン、プロペン及び１−ブテン）である。
【００２４】
これらのポリマーの中では、本発明は特に塩化ビニルホモポリマー及びコポリマーに関する。
【００２５】
本発明の強化用組成物は、熱可塑性ポリマー１００重量部に対して１〜１５部、好ましくは４〜９部の割合で使用する。
【００２６】
本発明は更に、前述のような熱可塑性ポリマー及び強化用組成物を含んでなる組成物に関する。
【００２７】
本発明は更に、処理もしくは加工条件及び／又は用途に応じて慣用的な添加剤（例えば顔料及び／又は充填剤、可塑剤、酸化防止剤、光又は紫外線安定剤）をも含んでいる組成物に関する。
【００２８】
これらの添加剤の例としては、β−ジケトン、ハイドロタルク石、ジヒドロピリジン、金属（例えばＬｉ，Ｎａ，Ｋ，Ｍｇ，Ｃａ，Ｓｒ，Ｂａ，Ｐｂ，Ｚｎ，Ｃｄ，Ｚｒ，Ａｌ，Ｓｉ，Ｓｂ，Ｂｉ）又はこれらの金属の対（例えばＣａ／Ｚｎ，Ｂａ／Ｃａ，Ｃａ／Ｃｄ，Ｂａ／Ｚｎ）のカルボン酸塩、メルカプチド（特にスズメルカプチド）、アルキル又はアリールホスファイト、エポキシ化合物、ポリオール、内部又は外部滑剤（例えばエステルろう、脂肪酸エステル、酸化又は非酸化ポリエチレンろう、水素化ヒマシ油、グリセロールモノオレエート又はステアレート、モンタン酸エステル）、並びに充填剤（例えば二酸化チタン又は炭酸カルシウム）を挙げることができる。
【００２９】
一般に熱可塑性ポリマーの１００重量％に達し得る割合で使用され得る可塑剤を除き、前述の他の添加剤は、熱可塑性ポリマーの０．０５〜２０重量％に相当し得る割合で使用することができる。
【００３０】
本発明の強化用組成物は、粒度の小さい粉末を良好に分散させる装置で組成物成分を単に乾式混合することにより製造することができる。このために、少なくとも５０００ｒｐｍ、好ましくは７０００〜１０，０００ｒｐｍの速度で回転するＣｌｏｕｐ型混合機を使用することができる。
【００３１】
衝撃添加剤及び沈降シリカは、前述の他の添加剤を使用するときにはこれらの添加剤の前でも同時でも後でも、混合物（強化用組成物）として又は別個のまま熱可塑性ポリマーに配合することができる。
【００３２】
沈降シリカは、特に噴霧によって実施され得る衝撃添加剤の乾燥時に導入することもできる。
【００３３】
【実施例】
以下の実施例で本発明を説明する。
【００３４】
本発明の強化用組成物の製造
以下の成分を用いて組成物を調製した。
【００３５】
衝撃添加剤
標準的な乳化重合技術を用いる米国特許第４ ２７８ ５７６号に記載の技術に従ってコア／シェルタイプ（８０／２０）の衝撃添加剤を調製した。即ち、７９．２部のブチルアクリレート、０．４部のブチレングリコールジアクリレート及び０．４部のジアリルマレエートをエラストマーコアとして使用し、次いで２０部のメチルメタクリレートを重合してコア／シェルアクリルポリマーを調製した。
【００３６】
エマルジョンを噴霧乾燥して粉末を得た。
【００３７】
添加剤の含水率は１％であった。
【００３８】
沈降シリカ
Ｓ１．ＮＥＯＳＩＬ ＧＰの商品名でＯＭＮＩＡ社から市販されている沈降シリカ。
【００３９】
Ｓ２．ＦＫ ５００ ＬＳの商品名でＤＥＧＵＳＳＡ社から市販されている沈降シリカ。
【００４０】
Ｓ３．ＦＫ ３２０ ＤＳの商品名でＤＥＧＵＳＳＡ社から市販されている沈降シリカ。
【００４１】
Ｓ４．ＳＩＰＥＲＮＡＴ Ｄ １７の商品名でＤＥＧＵＳＳＡ社から市販されている沈降シリカ。
【００４２】
Ｓ５．ＳＩＰＥＲＮＡＴ Ｄ １０の商品名でＤＥＧＵＳＳＡ社から市販されている沈降シリカ。
【００４３】
使用した沈降シリカの主要特性を以下の表１に示した。
【００４４】
【表１】
７０００ｒｐｍで回転する“Ｃｌｏｕｐ”タイプの混合機内で種々の成分を室温で乾式混合して、強化用組成物を製造した。
【００４６】
得られた混合物に関して、凝結試験及び流動性試験を実施した。
【００４７】
凝結試験
図１に示すような装置で試験を実施した。
【００４８】
６０×６０ｍｍで厚さ７ｍｍのＰＶＣプレート（１）上に、高さ５０ｍｍ、内径５５ｍｍの中空シリンダー（２）を置いた。
【００４９】
シリンダー（２）内に２０ｇの粉末を導入し、表面を平坦にして、直径５５ｍｍ、厚さ１０ｍｍのディスク（３）をはめた。このディスク上に、直径５０ｍｍ、高さ４０ｍｍのＰＶＣ中実シリンダー（４）、次いで８５×８５ｍｍ、厚さ６ｍｍのプレート（５）を置いた。
【００５０】
全体を４５℃の炉内に導入し、プレート（５）上に５ｋｇの重し（６）を置いた。
【００５１】
これらを４５℃で２時間維持した。
【００５２】
２時間後、５ｋｇの重し、プレート（５）及び中実シリンダー（４）を取り除いた。
【００５３】
材料を４５℃の炉内で更に３０分間維持し、次いで室温で３０分間圧縮粉末試料を冷却した。
【００５４】
圧縮タブレット形態の粉末を、振動状態（設定値５．５）にセットしたＰｒｏｌａｂｏタイプのスクリーニングユニットの１２−メッシュスクリーン（メッシュ寸法１．４０ｍｍ）内に導入した。
【００５５】
６０％の生成物が通過するまで、残留重量を５秒毎に記録した。
【００５６】
結果は秒で表す：
６０％の生成物の通過時間が長い程、凝結が進んでいる。
【００５７】
流動性試験はＩＳＯ国際規格６１８６−１９８０（Ｆ）に従って実施した。
【００５８】
結果は秒で表した。時間が長い程、流動性が悪い。
【００５９】
衝撃添加剤Ａ１と沈降シリカとを主成分とする強化用組成物で実施した凝結試験及び流動性試験の結果を表２に示す。
【００６０】
この表では、強化用組成物の成分比を重量％で表す。
【００６１】
【表２】
本発明の組成物の衝撃強さの評価
以下の成分（重量部）：
Ｋ値＝６７の塩化ビニルホモポリマー１００部、
亜燐酸鉛２．５部、
ステアリン酸カルシウム１．５部、
炭酸カルシウム６部、
ＴｉＯ2４部、
処理助剤（Ｍｅｔａｂｌｅｎ Ｂ．Ｖ社製Ｍｅｔａｂｌｅｎ Ｐ５５０）１部、１２ステアリン酸０．２部、
Ｌｏｘｉｏｌ Ｇ６０（内部滑剤）０．３部、
ポリエチレンろう（外部滑剤）４部及び本発明に包含されない例１の強化用組成物６部［→例８、表３］又は本発明に包含される例２の強化用組成物９部［→例９、表３］
を含む組成物を２５℃で調製した。
【００６３】
予め調製したＰＶＣ組成物から試験片を製造し、規格ＢＳ：２７８２に従ってノッチ付シャルピー衝撃強さ特性の測定試験を実施した。
【００６４】
シャルピー衝撃試験用試験片を製造するために、前述の成分を混合して得られたＰＶＣ樹脂組成物を、ＳＣＨＷＡＮＢＥＮＴＨＡＮタイプのカレンダーで、１７５℃で６分間圧延し、次いでＤＥＲＲＡＧＯＮプレスにて２００バールの圧力で５分間、１９０℃でプレート形状に成形し、前記プレートを加圧冷却した。
【００６５】
円形鋸、次いでシャルピー衝撃試験用カッターを用いて試験片を切断した。
【００６６】
上記規格によって規定された形状を示す試験片の厚さは２．５ｍｍである。
【００６７】
結果を表３に示す。
【００６８】
【表３】
沈降シリカを添加しても（例９）、ＰＶＣ組成物の衝撃強さが殆ど変化しないことが確認され得る。
【図面の簡単な説明】
【図１】凝結試験を実施するための装置を示す。
【符号の説明】
１ ＰＶＣプレート
２ 中空シリンダー
３ ディスク
４ 中実シリンダー
５ プレート[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a thermoplastic polymer reinforcing composition that exhibits improved anti-caking properties and fluidity and includes at least one precipitated silica.
[0002]
In particular, the present invention relates to vinyl chloride polymer reinforcing compositions that may include copolymers derived from butadiene and / or acrylate esters, and precipitated silica.
[0003]
[Prior art and problems to be solved by the invention]
Certain synthetic resins, especially those based on polyvinyl chloride or copolymers with a high vinyl chloride content, are widely used in the building industry, especially at low cost and because they exhibit good physical and / or chemical properties Has been.
[0004]
Nevertheless, the resin has a low impact strength at room temperature or low temperature, and the impact strength is low even after aging.
[0005]
It has been proposed to overcome these drawbacks by incorporating into the thermoplastic resin a material called impact additive, which is a polymer that generally exhibits some elastomeric properties.
[0006]
The weight of the elastomer in these impact additives can vary widely and is generally between 40% and 70%. However, even if it is desired to increase the weight of this elastomer in the impact additive to enhance the effect, considerable condensation is observed when the additive is isolated in powder form and also during storage.
[0007]
For this reason, handling becomes difficult, and transportation of the additive by an air conveyor becomes impossible.
[0008]
U.S. Pat. No. 3,985,703 describes a process which allows the production of core / shell acrylic polymer powders having an elastomer content of 55-85% and exhibiting improved anti-caking properties and flowability. .
[0009]
The method consists in adding 0.01 to 1.5% inert particles of ultrafine silica having a particle diameter of 0.012 microns, especially during spray drying of the powder.
[0010]
[Means for Solving the Problems]
Presently, thermoplastic polymer reinforcing compositions are known that contain at least one impact additive, exhibit improved anti-caking properties and fluidity, and further contain precipitated silica.
[0011]
DETAILED DESCRIPTION OF THE INVENTION
In the present invention, precipitated silica means silica in which primary particles of about 10 to 60 nm are associated to form an aggregate having an average size of 3 to 100 microns.
[0012]
Preference is given to using precipitated silica containing agglomerates with an average dimension of 3 to 80 microns, preferably 5 to 60 microns.
[0013]
The SiO 2 content measured for the material calcined at 1000 ° C. for 2 hours is 98% or more.
[0014]
According to the invention, a precipitated silica with a specific surface area (BET) of 25-700 m 2 / g, preferably 50-500 m 2 / g is used.
[0015]
According to the invention, both hydrophobic and hydrophilic precipitated silicas are used.
[0016]
Such precipitation of precipitated silica is described in the literature and is not the subject of the present invention.
[0017]
Examples of impact additives that can be used in the present invention include butadiene-styrene thermoplastic resins (eg, acrylonitrile-butadiene-styrene resin (ABS resin), methacrylic acid alkyl ester-butadiene-styrene resin (MBS resin)), and acrylic acid. And / or graft copolymers derived from conjugated dienes such as butadiene or isoprene selected from among (methacrylic acid alkyl ester-butadiene-styrene resin). Among the alkyl methacrylate resins, mention may be made in particular of methyl methacrylate-butadiene-styrene resins, ethyl methacrylate-butadiene-styrene resins, butyl methacrylate-butadiene-styrene resins and lauryl methacrylate-butadiene-styrene resins. With respect to the acrylic acid alkyl ester-butadiene-styrene resin, mention may be made of resins derived from methyl, ethyl, butyl or 2-ethylhexyl acrylate. Further, a graft copolymer in which a chain of a copolymer of C 1 -C 4 alkyl methacrylate and C 1 -C 8 alkyl acrylate is grafted to a main chain composed of a random copolymer of a conjugated diene and a C 2 -C 12 alkyl acrylate. Can be mentioned. The main chain copolymer may further comprise units derived from a crosslinker comprising at least two CH 2 ═C <groups. This copolymer is described, for example, in French Patent Nos. 2 551 446 and 2 551 447, the contents of which are incorporated herein by reference.
[0018]
Thermoplastic resins such as styrene-butadiene rubber (SBR), nitrile-butadiene rubber (NBR) and acrylate-butadiene rubber (ABR) can be used during processing and before vulcanization.
[0019]
Of these polymers derived from butadiene, MBS and ABS resins are preferred.
[0020]
It is also possible to use essentially acrylic resins, ie resins containing 90% by weight or more of polymerized acrylic ester.
[0021]
According to the invention, the elastomer content in the polymer impact additive is at least 60% by weight, preferably 70-90% by weight.
[0022]
The reinforcing composition of the present invention comprises at least 80 wt%, preferably 95-99 wt% impact additive, and no more than 20 wt%, preferably 1-5 wt% precipitated silica.
[0023]
Thermoplastic polymers that can be blended with the precipitated silica of the present invention to improve impact strength are in particular polycondensate type polymers (especially polyesters such as polybutylene terephthalate, polycarbonates, polyamides) or eg polymethacrylates, in particular polymethylmethacrylate. It can consist of a polymer type polymer such as The thermoplastic polymer is obtained by copolymerization of vinyl chloride homopolymer, which may optionally be perchlorinated, and vinyl chloride and one or more ethylenically unsaturated comonomers, and contains at least 80% by weight of polymerized vinyl chloride. It may consist of one or more addition polymers selected from the group consisting of existing copolymers. Particularly suitable comonomers for the preparation of such copolymers are vinylidene halides (eg vinylidene chloride or vinylidene fluoride), vinyl carboxylates (eg vinyl acetate, vinyl propionate and vinyl butyrate), acrylic acid and methacrylic acid, derived therefrom. Nitriles, amides and alkyl esters (especially acrylonitrile, acrylamide, methacrylamide, methyl methacrylate, methyl acrylate, butyl acrylate, ethyl acrylate, 2-ethylhexyl acrylate), vinyl aromatic derivatives (eg styrene and vinyl naltalene), and olefins (For example, bicyclo (2.2.1) -2-heptene, bicyclo (2.2.1) hepta-2,5-diene, ethylene, propene and 1-butene).
[0024]
Among these polymers, the present invention particularly relates to vinyl chloride homopolymers and copolymers.
[0025]
The reinforcing composition of the present invention is used in a ratio of 1 to 15 parts, preferably 4 to 9 parts, per 100 parts by weight of the thermoplastic polymer.
[0026]
The invention further relates to a composition comprising a thermoplastic polymer as described above and a reinforcing composition.
[0027]
The present invention further comprises compositions that include conventional additives (eg, pigments and / or fillers, plasticizers, antioxidants, light or UV stabilizers) depending on processing or processing conditions and / or applications. About.
[0028]
Examples of these additives include β-diketone, hydrotalcite, dihydropyridine, metal (eg, Li, Na, K, Mg, Ca, Sr, Ba, Pb, Zn, Cd, Zr, Al, Si, Sb, Bi) or carboxylates of these metal pairs (eg Ca / Zn, Ba / Ca, Ca / Cd, Ba / Zn), mercaptides (especially tin mercaptides), alkyl or aryl phosphites, epoxy compounds, polyols, internal or To mention external lubricants (eg ester waxes, fatty acid esters, oxidized or non-oxidized polyethylene waxes, hydrogenated castor oil, glycerol monooleate or stearate, montanates) and fillers (eg titanium dioxide or calcium carbonate). it can.
[0029]
Except for plasticizers that can generally be used in proportions that can reach 100% by weight of the thermoplastic polymer, the other additives mentioned above can be used in proportions that can correspond to 0.05 to 20% by weight of the thermoplastic polymer. it can.
[0030]
The reinforcing composition of the present invention can be produced by simply dry-mixing the composition components in an apparatus that satisfactorily disperses a powder having a small particle size. For this, it is possible to use a Loop-type mixer that rotates at a speed of at least 5000 rpm, preferably 7000-10,000 rpm.
[0031]
The impact additive and precipitated silica may be incorporated into the thermoplastic polymer as a mixture (strengthening composition) or separately, either before, simultaneously with, or after these additives when using the other additives described above. it can.
[0032]
Precipitated silica can also be introduced during the drying of impact additives, which can be carried out in particular by spraying.
[0033]
【Example】
The following examples illustrate the invention.
[0034]
Production of the reinforcing composition of the present invention A composition was prepared using the following ingredients.
[0035]
Impact Additive A core / shell type (80/20) impact additive was prepared according to the technique described in U.S. Pat. No. 4,278,576 using standard emulsion polymerization techniques. That is, 79.2 parts butyl acrylate, 0.4 parts butylene glycol diacrylate and 0.4 parts diallyl maleate were used as the elastomer core, and then 20 parts methyl methacrylate was polymerized to produce a core / shell acrylic polymer. Was prepared.
[0036]
The emulsion was spray dried to obtain a powder.
[0037]
The water content of the additive was 1%.
[0038]
Precipitated silica S1. Precipitated silica commercially available from OMNIA under the name NEOSIL GP.
[0039]
S2. Precipitated silica commercially available from DEGUSSA under the trade name FK 500 LS.
[0040]
S3. Precipitated silica commercially available from DEGUSSA under the trade name FK 320 DS.
[0041]
S4. Precipitated silica commercially available from DEGUSSA under the trade name SIPERNAT D17.
[0042]
S5. Precipitated silica commercially available from DEGUSSA under the trade name SIPERNAT D10.
[0043]
The main characteristics of the precipitated silica used are shown in Table 1 below.
[0044]
[Table 1]
Various components were dry mixed at room temperature in a “Cloop” type mixer rotating at 7000 rpm to produce a reinforcing composition.
[0046]
A set test and a fluidity test were performed on the obtained mixture.
[0047]
Coagulation test The test was carried out with an apparatus as shown in Fig. 1.
[0048]
A hollow cylinder (2) having a height of 50 mm and an inner diameter of 55 mm was placed on a PVC plate (1) of 60 × 60 mm and a thickness of 7 mm.
[0049]
20 g of powder was introduced into the cylinder (2), the surface was flattened, and a disc (3) having a diameter of 55 mm and a thickness of 10 mm was fitted. On this disc was placed a PVC solid cylinder (4) having a diameter of 50 mm and a height of 40 mm, and then a plate (5) having a size of 85 × 85 mm and a thickness of 6 mm.
[0050]
The whole was introduced into a 45 ° C. oven and a 5 kg weight (6) was placed on the plate (5).
[0051]
These were maintained at 45 ° C. for 2 hours.
[0052]
After 2 hours, a 5 kg weight was removed and the plate (5) and solid cylinder (4) were removed.
[0053]
The material was maintained in a 45 ° C. oven for an additional 30 minutes, and then the compressed powder sample was cooled for 30 minutes at room temperature.
[0054]
The powder in the form of a compressed tablet was introduced into a 12-mesh screen (mesh size 1.40 mm) of a Prolabo type screening unit set in a vibrating state (set value 5.5).
[0055]
Residual weight was recorded every 5 seconds until 60% of the product had passed.
[0056]
The result is expressed in seconds:
The longer the 60% product transit time, the more congealed.
[0057]
The fluidity test was performed according to ISO international standard 6186-1980 (F).
[0058]
The result was expressed in seconds. The longer the time, the worse the fluidity.
[0059]
Table 2 shows the results of a setting test and a fluidity test performed on the reinforcing composition mainly composed of impact additive A1 and precipitated silica.
[0060]
In this table, the component ratio of the reinforcing composition is expressed in weight%.
[0061]
[Table 2]
Evaluation of impact strength of the composition of the present invention The following components (parts by weight):
100 parts of a vinyl chloride homopolymer with a K value = 67,
2.5 parts of lead phosphite,
1.5 parts of calcium stearate,
6 parts of calcium carbonate,
4 parts of TiO 2
1 part of processing aid (Metablen P550 manufactured by Metablen BV), 12 parts of 12 stearic acid,
Loxiol G60 (internal lubricant) 0.3 part,
4 parts of polyethylene wax (external lubricant) and 6 parts of the reinforcing composition of Example 1 not included in the present invention [→ Example 8, Table 3] or 9 parts of the reinforcing composition of Example 2 included in the present invention [→ Example 9, Table 3]
A composition containing was prepared at 25 ° C.
[0063]
A test piece was manufactured from a PVC composition prepared in advance, and a measurement test of notched Charpy impact strength characteristics was performed according to the standard BS: 2782.
[0064]
In order to produce a specimen for Charpy impact test, a PVC resin composition obtained by mixing the above-mentioned components was rolled on a SCHWANBENTHAN type calendar at 175 ° C. for 6 minutes, and then in a DERRAGON press at 200 bar. The plate was molded into a plate shape at 190 ° C. for 5 minutes under pressure, and the plate was pressurized and cooled.
[0065]
The specimen was cut using a circular saw and then a Charpy impact test cutter.
[0066]
The thickness of the test piece showing the shape defined by the above standard is 2.5 mm.
[0067]
The results are shown in Table 3.
[0068]
[Table 3]
It can be seen that even when precipitated silica is added (Example 9), the impact strength of the PVC composition hardly changes.
[Brief description of the drawings]
FIG. 1 shows an apparatus for performing a setting test.
[Explanation of symbols]
1
Claims (12)
沈降シリカのＳｉＯ ２ 含量が、１０００℃で２時間焼成した沈降シリカに対して測定して、９８％より大きく、
沈降シリカのＢＥＴ比表面積が２５〜７００ｍ２／ｇであることを特徴とする熱可塑性ポリマー強化用組成物。At least 80% by weight of at least one polymer impact additive having an elastomer content of 60% by weight or more and 20% by weight or less of precipitated silica, the precipitated silica being bonded to an average dimension of 3 to 3%. Consisting of 10-60 nm primary particles forming 100 μm aggregates,
The SiO 2 content of the precipitated silica is greater than 98% as measured against precipitated silica calcined at 1000 ° C. for 2 hours ,
A composition for reinforcing a thermoplastic polymer, wherein the precipitated silica has a BET specific surface area of 25 to 700 m 2 / g.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR9411898A FR2725453B1 (en) | 1994-10-05 | 1994-10-05 | REINFORCING COMPOSITIONS COMPRISING PRECIPITATED SILICA FOR THERMOPLASTIC POLYMERS HAVING IMPROVED ANTI-CUSTING AND FLOW PROPERTIES |
| FR9411898 | 1994-10-05 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH08113669A JPH08113669A (en) | 1996-05-07 |
| JP3894968B2 true JP3894968B2 (en) | 2007-03-22 |
Family
ID=9467588
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP25869095A Expired - Fee Related JP3894968B2 (en) | 1994-10-05 | 1995-10-05 | Composition for reinforcing thermoplastic polymers exhibiting improved anti-caking properties and fluidity comprising precipitated silica |
Country Status (8)
| Country | Link |
|---|---|
| US (1) | US5763515A (en) |
| EP (1) | EP0705876B1 (en) |
| JP (1) | JP3894968B2 (en) |
| AT (1) | ATE248889T1 (en) |
| CA (1) | CA2159875C (en) |
| DE (1) | DE69531649T2 (en) |
| ES (1) | ES2206483T3 (en) |
| FR (1) | FR2725453B1 (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001262073A (en) * | 2000-03-01 | 2001-09-26 | Clariant Gmbh | Preparation of pigmented powder coating material |
| FR2810987B1 (en) * | 2000-07-03 | 2002-08-16 | Rhodianyl | POLYMERIC COMPOSITIONS WITH IMPROVED MECHANICAL PROPERTIES |
| US20020197823A1 (en) * | 2001-05-18 | 2002-12-26 | Yoo Jae-Yoon | Isolation method for semiconductor device |
| JP5100937B2 (en) † | 2001-08-10 | 2012-12-19 | ローム アンド ハース カンパニー | Thermoplastic resin composition with less plate-out |
| CN102863727B (en) * | 2012-10-25 | 2014-07-09 | 河北盛华化工有限公司 | Production method of rigid polyvinyl chloride plastic sheet by using high impact polyvinyl chloride (PVC) composite resin HI5 |
| CN102863728B (en) * | 2012-10-25 | 2014-07-09 | 河北盛华化工有限公司 | Production method of high impact polyvinyl chloride (PVC) composite resin H17 tray |
| CN102863729B (en) * | 2012-10-25 | 2014-07-09 | 河北盛华化工有限公司 | Production method of high impact polyvinyl chloride (PVC) composite resin HI7 well cover |
| CN113861592B (en) * | 2021-11-08 | 2023-03-21 | 江苏金材科技有限公司 | Ultrathin high-toughness net structure reinforced composite base material and preparation method thereof |
Family Cites Families (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3873489A (en) * | 1971-08-17 | 1975-03-25 | Degussa | Rubber compositions containing silica and an organosilane |
| US3985703A (en) | 1975-06-24 | 1976-10-12 | Rohm And Haas Company | Process for manufacture of acrylic core/shell polymers |
| CA1094720A (en) * | 1977-04-14 | 1981-01-27 | Polysar Limited | Silica filled vulcanizates |
| US4278576A (en) | 1978-12-05 | 1981-07-14 | Rohm And Haas Company | Isolation and improvement of impact modifier polymer powders |
| US4519430A (en) * | 1982-07-29 | 1985-05-28 | The B. F. Goodrich Company | Energy saving tire with silica-rich tread |
| FR2551446B1 (en) | 1983-08-31 | 1987-03-20 | Elf Aquitaine | RESIN COMPOSITIONS HAVING IMPROVED IMPACT RESISTANCE CONTAINING A THERMOPLASTIC POLYMER, A SHOCK ADDTIVE OF THE GRAFT COPOLYMER TYPE, AND POSSIBLY OTHER ADDITIVES, AND CORRESPONDING GRAFT COPOLYMER, WITH THE CHARACTER OF SHOCK ADDITIVE |
| FR2551447B1 (en) | 1983-08-31 | 1987-03-27 | Elf Aquitaine | RESIN COMPOSITIONS HAVING IMPROVED IMPACT RESISTANCE CONTAINING A THERMOPLASTIC POLYMER, A SHOCK ADDTIVE OF THE GRAFT COPOLYMER TYPE, AND POSSIBLY OTHER ADDITIVES, AND CORRESPONDING GRAFT COPOLYMER, WITH THE CHARACTER OF SHOCK ADDITIVE |
| FR2589871B1 (en) * | 1985-09-13 | 1987-12-11 | Rhone Poulenc Chim Base | REINFORCING FILLER FOR SILICA-BASED ELASTOMER |
| DE3628320A1 (en) * | 1986-08-21 | 1988-02-25 | Bayer Ag | HYDROPHOBIC PIGMENTS AND FILLERS FOR INTRODUCTION IN PLASTICS |
| US4792487A (en) * | 1987-03-12 | 1988-12-20 | James River Corporation Of Virginia | Ink jet recording medium comprising (a) water expansible colloidal clay (b) silica and (c) water insoluble synthetic binder |
| US4956398A (en) * | 1989-06-07 | 1990-09-11 | Polysar Limited | Nitrile rubber/vinyl chloride polymer/silica compositions |
| US5094829A (en) * | 1990-06-21 | 1992-03-10 | Ppg Industries, Inc. | Reinforced precipitated silica |
| FR2673187B1 (en) * | 1991-02-25 | 1994-07-01 | Michelin & Cie | RUBBER COMPOSITION AND TIRE COVERS BASED ON SAID COMPOSITION. |
| DE4202023A1 (en) * | 1992-01-25 | 1993-07-29 | Degussa | HAFTPROMOTER FOR RUBBER AND PLASTIC MIXTURES |
| JP2688466B2 (en) * | 1993-01-08 | 1997-12-10 | 信越化学工業株式会社 | Acrylic silicone rubber composition and cured product thereof |
| CA2105334C (en) * | 1993-04-02 | 2004-03-30 | Jean Bergh | Tire with silica reinforced tread |
-
1994
- 1994-10-05 FR FR9411898A patent/FR2725453B1/en not_active Expired - Fee Related
-
1995
- 1995-09-28 AT AT95402181T patent/ATE248889T1/en not_active IP Right Cessation
- 1995-09-28 DE DE69531649T patent/DE69531649T2/en not_active Expired - Lifetime
- 1995-09-28 ES ES95402181T patent/ES2206483T3/en not_active Expired - Lifetime
- 1995-09-28 EP EP95402181A patent/EP0705876B1/en not_active Expired - Lifetime
- 1995-10-04 CA CA002159875A patent/CA2159875C/en not_active Expired - Fee Related
- 1995-10-05 JP JP25869095A patent/JP3894968B2/en not_active Expired - Fee Related
- 1995-10-05 US US08/539,634 patent/US5763515A/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| CA2159875C (en) | 2007-05-29 |
| DE69531649D1 (en) | 2003-10-09 |
| ES2206483T3 (en) | 2004-05-16 |
| EP0705876B1 (en) | 2003-09-03 |
| FR2725453A1 (en) | 1996-04-12 |
| ATE248889T1 (en) | 2003-09-15 |
| EP0705876A1 (en) | 1996-04-10 |
| DE69531649T2 (en) | 2004-07-08 |
| CA2159875A1 (en) | 1996-04-06 |
| FR2725453B1 (en) | 1996-11-08 |
| US5763515A (en) | 1998-06-09 |
| JPH08113669A (en) | 1996-05-07 |
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